KR20080034501A - Fiber network layers and flexible penetration resistant articles comprising the same - Google Patents

Abstract

The present invention relates to a first plurality of yarns and a second plurality of yarns in which each of the first and second yarns are disposed in a first direction parallel or substantially parallel to the other first and second yarns, and The third yarns have a third plurality of yarns disposed in a second direction parallel or substantially parallel to the other third yarns; The second direction relates to a fibrous network layer for use in a penetration resistant article that intersects with the first direction. The third yarns and the first yarns or the second yarns are made of the first polymer. The specific strength of each of the first, second and third yarns is at least 15 g / dtex. The layers may be (i) made of a second polymer where the second yarns are different from the first polymer, or (ii) the average linear density of the first yarns is different from the average linear density of the second yarns, or (iii) the first and second yarns. The multifilament yarns with these filaments, and the average linear density of the filaments of the first yarns is different from the filaments of the second yarns, or (iv) they are combined.

Penetration resistant article, fiber network layer

Description

FIBER NETWORK LAYERS AND FLEXIBLE PENETRATION RESISTANT ARTICLES COMPRISING SAME

<Related application>

This application claims the benefit of US Provisional Application No. 60 / 707,200, filed August 10, 2005, and US Provisional Application No. 60 / 720,898, filed September 27, 2005, the entire disclosure of which is incorporated herein by reference. .

The present invention relates to a fiber network layer for use in a penetration resistant article, and to an article containing one or more such layers.

It has been reported that the ballistic performance of antiballistic vests made from 100% poly (p-phenylene-2,6-benzobisoxazole) fabrics (PBO fabrics) may be higher than conventional fabrics. have. However, PBO fabrics are very expensive and are limited for use for some life protection applications.

For antiballistic materials, various fabric configurations are known. For example, it is known to use different layers of fibers of a first polymer and a second layer of fibers of a different polymer.

It is also known that fibers of two polymers can be used in a single layer. For example, Canadian Patent Application No. 1034842 teaches composite woven protective fabrics woven with asymmetrical woven fabrics using warp and weft fibers of different properties. Another published application, Canadian Patent Application 2313995, teaches a woven fabric in which two adjacent fibers are different materials in both warp and weft.

US Pat. No. 6,155,306 teaches multifilament bulletproof fabrics that may have warp yarns with polyethylene fibers and weft yarns including aramid fibers. U. S. Patent No. 6,610, 619 teaches a first set of yarns that intersect a second set of yarns, and teaches multi-layer cross-layer fabrics in which the ratio of linear density of the first set of yarns to the second set of yarns is greater than 4.2. . U.S. Patent No. 5,180,880 teaches a soft vest in which different materials are warp aramid and weft thermoplastic. European Patent Application No. 310199 (A1) teaches ballistic woven fabrics with different materials in the warp and weft directions. U.S. Patent 5,187,003 discloses woven antiballistic fabrics in which the elongation at break of the fibers in the weft direction is greater than the fibers in the warp direction.

Despite the above developments, there is a need for lighter weight and higher performance of life protective clothing.

<Overview of invention>

The present invention

A first plurality of yarns and a second plurality of yarns in which each of the first and second yarns are arranged in a first direction parallel or substantially parallel to the other first and second yarns; And

A third plurality of yarns, each of the third yarns being arranged in a second direction parallel or substantially parallel to the other third yarns, wherein the second direction intersects the first direction, and the third The yarns, and the first yarns or the second yarns are made of a first polymer;

The tenacity of each of the first, second and third yarns is at least about 15 g / dtex (preferably 20 to 45 g / dtex in some embodiments),

(i) the second yarns are made of a second polymer different from the first polymer, (ii) the average linear density of the first yarns is different from the average linear density of the second yarns, or (iii) the first and second yarns are filaments Permeable multifilament yarns, the average linear density of the filaments of the first yarns being different from the filaments of the second yarns, or (iv) a combination .

In some preferred embodiments, the fiber network layer further comprises a fourth plurality of yarns, each fourth yarn being disposed in a second direction parallel or substantially parallel to the third yarns, and (i) 4 yarns are made of a second polymer or a third polymer, (ii) the average linear density of the third yarns is different from the average linear density of the fourth yarns, or (iii) the third and fourth yarns are multifilament yarns with filaments , The average linear density of the filaments of the third yarns is different from the filaments of the fourth yarns, or (iv) they are combined.

In certain embodiments, the first yarns comprise at least 35% of the total number of yarns in the first direction (preferably between 40 and 60% in some embodiments), and the second yarns comprise the entirety of the yarns in the first direction At least 35% (preferably between 40 and 60% in some embodiments) of the number.

In some embodiments, all the fibers in the second direction are third plurality of yarns.

In some fiber networks, the area density of the fiber network layer is 10 kg / m 2 or less. In some embodiments, the area density is preferably 2 to 8 kg / m 2.

In certain embodiments of the present invention, each of the first, second and third yarns has an elongation at break of at least 2% (preferably between 2.5% and 10% in some embodiments) and an elastic modulus of at least 150 g per dtex ( Preferably, in some embodiments, 250 to 2000 g per dtex).

Certain layers are those wherein the specific strength of each of the first, second and third yarns is at least 15 g per denier (preferably at least 20 g per denier in some embodiments). In another embodiment, the fiber network layer has a specific strength of at least one of the first, second and third yarns of at least 30 g per denier. In some embodiments, the specific strength is preferably at least 35 g per denier.

Some layers have at least one of the first, second and third yarns having a specific strength of at least 30 g per denier and a density of at least 1.6 g per cm 3.

In some embodiments, the second yarns are made of a second polymer different from the first polymer.

In certain embodiments, the average linear density of the first yarns is different from the average linear density of the second yarns. In some embodiments, the first and second yarns comprise multifilament yarns with filaments, the average linear density of the filaments of the first yarns being different from the filaments of the second yarns.

In some embodiments, the present invention is directed to a fibrous network layer wherein the first and third yarns are made of the first polymer and the average linear density is substantially the same, and the filaments of the first and third yarns are substantially the same average linear density.

In some layers, the linear density of each of the first, second and third yarns is between 100 and 5000 decitex. In some embodiments, the linear density is preferably 220 to 3300 decitex. In certain layers, the linear density of the first, second and third yarns is between 0.1 and 10 decitex. In certain embodiments, the yarns are preferably 0.2 to 5.5 decitex.

Some layers of the present invention include filaments of first, second and third yarns that are continuous filaments, staple fibers or a mixture of both.

In some embodiments, the first and second threads are arranged in alternating order.

In some embodiments, the first and second polymers are polyamides, polyolefins, polybenzoxazoles, polybenzothiazoles, poly {2,6-diimidazo [4,5-b: 4 ', 5'-e ] Pyridinylene-1,4- (2,5-dihydroxy) phenylene}, polyarenazole, polypyridazole, polypyridobisimidazole and mixtures thereof. In certain embodiments, the first polymer is poly (p-phenylene terephthalamide).

Some layers of the present invention are unidirectional arrays in which the first yarns, the second yarns and the third yarns are stacked at right angles on a woven, nonwoven, or unidirectional arrangement.

The invention also relates to a flexible, penetration resistant article comprising a plurality of fibrous network layers described herein. Some flexible penetration resistant articles have an area density of 2-12 kg / m 2. Certain articles are impregnated with at least one of the fabric layers a polymeric matrix comprising a thermoplastic, thermoset or a mixture thereof.

Also in some embodiments, the present invention relates to a method of weaving fiber networks.

In one embodiment, the method of making the fiber network layer is

A first plurality of yarns and a second plurality of yarns in which the first and second yarns are arranged in a first direction parallel to or substantially parallel to the other first and second yarns;

Weaving the third plurality of yarns with each third yarn disposed in a second direction parallel or substantially parallel to the other third yarns, where the second direction intersects with the first direction and , The third yarns, and the first yarns or the second yarns are made of the first polymer;

The specific strength of each of the first, second and third yarns is at least 15 g / dtex,

(i) the second yarns are made of a second polymer different from the first polymer, (ii) the average linear density of the first yarns is different from the average linear density of the second yarns, or (iii) the first and second yarns Multifilament yarns with filaments, the average linear density of the filaments of the first yarns being different from the filaments of the second yarns, or (iv) they are combined.

In certain embodiments, the method further comprises weaving a fourth plurality of yarns in which each fourth yarn is disposed in a second direction parallel or substantially parallel to the third yarns,

(i) the fourth yarns are made of a second polymer or a third polymer, (ii) the average linear density of the third yarns is different from the average linear density of the fourth yarns, or (iii) the third and fourth yarns are Wherein the filaments of the third yarns differ from the filaments of the fourth yarns, or (iv) they are combined.

1 is an illustration of a woven fabric with first and second yarns in a first direction and a third yarn in a second direction.

FIG. 2 is an illustration of a woven fabric with first and second yarns in a first direction and third and fourth yarns in a second direction.

The invention may be more readily understood by reference to the following detailed description of exemplary and preferred embodiments forming part of this application. The claims are not limited to the specific devices, methods, conditions or parameters described and / or described herein, and the terminology used herein is for the purpose of describing particular embodiments only by way of example and to limit the invention as claimed. It is important to understand that it is not intended. Also, unless expressly indicated otherwise, the singular forms used herein, including the appended claims, include plural and reference to a specific numerical value includes at least that specific value. When a range of values is shown, another embodiment includes values from one particular value to another particular value or from one particular value or to another particular value. Likewise, where a value is approximated using the antecedent “about,” a particular value will be interpreted to form another embodiment. All ranges are included and combinable.

Preferably, the penetration resistant composites and articles of the present invention comprise a plurality of fibrous layers made from polymeric fibers.

For the purposes herein, the term “fiber” is defined as an object that is relatively flexible, macrohomogeneously, and has a high ratio of length to width across a cross section perpendicular to the length. The fiber cross section may be of any shape, but is typically circular. The fibers may be in uncoated or coated form or other pretreated (eg, predrawn or heat treated) form. As used herein, the term “filament” is used interchangeably with the term “fiber”.

"Thread" as defined herein refers to two or more fibers that are continuous in length, and the fibers are as described above.

For the purposes herein, "fabric" refers to any woven, knitted or nonwoven structure. "Weaving" means any weaving weave, such as plain weave, crowfoot weave, basket weave, runner weave, twill weave, and the like. "Knitting" means a structure made by interlooping or intermeshing one or more yarns, fibers or multifilament yarns. "Nonwoven" means a network of fibers, including unidirectional fibers, felt, and the like.

The fibrous layers can have a number of shapes, including but not limited to knitted or woven fabrics or nonwoven structures. Nonwoven refers to a network of fibers, including unidirectional (when contained in a matrix resin) felt and the like. Weaving means any woven fabric, such as plain weave, crowfoot weave, basket weave, runner weave, twill weave, and the like. Plain weave is considered the most common weaving used in goods.

In some preferred embodiments, the fabric is made by weaving a plurality of yarns.

The area density of the fabric layer is determined by measuring the weight of each single layer of the selected size (eg 10 cm × 10 cm). The area density of the composite structure is determined by the sum of the area densities of the individual layers.

Denier is determined according to ASTM D 1577 and is the linear density of the fiber, specified as weight (g) of fiber 9000 m.

Specific strength is determined according to ASTM D 885 and is the maximum or fracture stress of the fiber, specified as g per denier.

A wide range of suitable thermosetting and thermoplastic resins and mixtures thereof are well known in the art and can be used as matrix material. For example, the thermoplastic resin may include one or more polyurethanes, polyimides, polyethylenes, polyesters, polyether ether ketones, polyamides, polycarbonates, and the like. The thermosetting resin may be at least one epoxy based resin, polyester based resin, phenol based resin, or the like, preferably polyvinyl butyral phenol resin. The mixture can be any combination of thermoplastic resins and thermosetting resins.

Exemplary lists of suitable fibers for the present invention include polyamide fibers, polyolefin fibers, polybenzoxazole fibers, polybenzothiazole fibers, poly {2,6-diimidaz [4,5-b: 4 ', 5 '-e] pyridinylene-1,4- (2,5-dihydroxy) phenylene} (PIPD) fibers, or mixtures thereof. Preferably, the fiber is poly {2,6-diimidazo [4,5-b: 4 ', 5'-e] pyridinylene-1,4- (2,5-dihydroxy) phenylene} (PIPD) is made of fibers.

If the polymer is polyamide, aramid is preferred. "Aramid" means polyamide in which at least 85% of the amide (-CO-NH-) linkages are directly attached to two aromatic rings. Suitable aramid fibers are described in Man-Made Fibers-Science and Technology, Volume 2, Section titled Fiber-Forming Aromatic Polyamides, page 297, W. Black et al., Interscience Publishers, 1968. Aramid fibers can also be found in US Pat. No. 4,172,938; 3,869,429; 3,819,587; 3,673,143; 3,354,127; And 3,094,511. Additives may be used with the aramid and up to 10 wt% of other polymeric materials may be blended with the aramid, or other dichlorides containing up to 10 percent other diamines substituting the diamines of the aramids or substituting diacid chlorides of the aramids It has been found that copolymers containing up to 10% can be used.

Preferred aramids are para-aramids, with poly (p-phenylene terephthalamide) (PPD-T) being the preferred para-aramid. PPD-T is a homopolymer produced by approximately molar to mole polymerization of p-phenylene diamine and terephthaloyl chloride, and also a small amount of other diamine and p-phenylene diamine and a small amount of other diacid chloride and terephthaloyl chloride. It means the copolymer produced by incorporation. Typically, other diamines and other diacid chlorides may be used in amounts up to about 10 mol% of p-phenylene diamine or terephthaloyl chloride or in amounts slightly above, provided that such other diamines and diacid chlorides interfere with the polymerization reaction. There should be no reactive groups. PPD-T also contains other aromatic diamines and other aromatic diacid chlorides, such as 2,6-naphthaloyl chloride or chloroterephthaloyl chloride or dichloroterephthaloyl chloride or 3,4'-diaminodiphenylether. It means the copolymer produced by incorporation.

If the polymer is a polyolefin, polyethylene or polypropylene is preferred. Polyethylenes may contain small amounts of chain branching agents or may contain up to 5 comonomers of up to 5 modifying units per 100 main chain carbon atoms and may also contain up to about 50% by weight of alken-1-polymers, especially low density polyethylene , Low molecular weight additives such as antioxidants, lubricants, sunscreens, colorants, etc., which are commonly incorporated, or one or more polymer additives, such as propylene, or the like, and are preferably linear linear polyethylene materials having a molecular weight it means. This is commonly known as extended chain polyethylene (ECPE). Likewise, polypropylene is preferably a polypropylene material having a molecular weight greater than 1000000 and mainly linear. High molecular weight linear polyolefin fibers are commercially available. The preparation of polyolefin fibers is discussed in US Pat. No. 4,457,985.

Polyarenazole polymers can be prepared by reacting a mixture of dry ingredients with a polyphosphoric acid (PPA) solution. Dry ingredients may include azole forming monomers and metal powders. Accurately weighed batches of such dry ingredients can be obtained using at least some of the preferred embodiments of the present invention.

Examples of azole forming monomers include 2,5-dimercapto-p-phenylene diamine, terephthalic acid, bis (4-benzoic acid), oxybis (4-benzoic acid), 2,5-dihydroxyterephthalic acid, isophthalic acid, 2, 5-pyridodicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,6-quinolinedicarboxylic acid, 2,6-bis (4-carboxyphenyl) pyridobisimidazole, 2,3, 5,6-tetraaminopyridine, 4,6-diaminoresosinol, 2,5-diaminohydroquinone, 1,4-diamino-2,5-dithiobenzene or any combination thereof. Preferably, the azole forming monomers comprise 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid. In certain embodiments, it is preferred to phosphorylate azole forming monomers. Preferably, the phosphorylated azole forming monomer is polymerized in the presence of polyphosphoric acid and a metal catalyst.

To set the molecular weight of the final polymer, metal powder can be used. Typically, metal powders include iron powders, tin powders, vanadium powders, chromium powders and any combination thereof.

After mixing the azole forming monomer and the metal powder, the mixture is reacted with polyphosphoric acid to form a polyarenazole polymer solution. If desired, additional polyphosphoric acid can be added to the polymer solution. Typically, the polymer solution is extruded or spun through a die or spinneret to produce or spun filaments.

Polybenzoxazole (PBO) and polybenzothiazole (PBZ) are two suitable polymers. Such polymers are described in international patent WO 93/20400. Preferably, the polybenzoxazole and polybenzothiazole consist of repeating units of the following structure.

In the above, the aromatic group bonded to the nitrogen atom may be heterocyclic, preferably carbocyclic; It may be a fused or unfused polycyclic system and is preferably a single six membered ring. The groups in the main chain of bisazole are preferably para-phenylene groups, which may be replaced by divalent organic groups which do not interfere with the preparation of the polymer, or may be free of groups at all. For example, the group may be aliphatic, tolylene, biphenylene, bisphenylene ether or the like having 12 or less carbon atoms.

The polybenzoxazoles and polybenzothiazoles used to make the fibers of the present invention should have at least 25, preferably at least 100 repeat units. The preparation of the polymer and the spinning of the polymer are disclosed in the aforementioned international patent WO 93/20400.

M5 fibers are suitable for use in the present invention. Such fibers are based on poly [diimidazo pyridinylene (dihydroxy) phenylene]. M5 fibers are known to have an average modulus of about 310 GPa and an average specific strength of about 5.8 GPa or less. M5 fibers are described in Brew, et al., Composites Science and Technology 1999, 59, 1109; Van der Jagt and Beukers, Polymer 1999, 40, 1035; Sikkema, Polymer 1998, 39, 5981; Klop and Lammers, Polymer, 1998, 39, 5987; Hageman, et al., Polymer 1999, 40, 1313.

The laminated layer is defined as a network of fibers impregnated with a polymer matrix comprising a thermoset or thermoplastic resin or mixtures thereof. Each layer is added to the thickness and weight of the composite structure, thereby reducing the flexibility, fit and comfort of the composite structure. Thus, the number of layers is chosen such that the entire composite structure is designed and used to protect against a particular threat.

The layers may be held or joined together in any manner, for example by sewing together, or may be laminated and held together, for example in a fabric envelope or carrier. The layers forming the part may be laminated and combined separately, or all the plurality of layers may be stacked and combined as a single unit.

The layers can also be held together by a polymer matrix comprising a thermoset or thermoplastic resin or mixtures thereof. A wide range of suitable thermosetting and thermoplastic resins and mixtures thereof are well known in the art and can be used as matrix material. For example, the thermoplastic resin may include one or more polyurethanes, polyimides, polyethylenes, polyesters, polyether ether ketones, polyamides, polycarbonates, and the like. The thermosetting resin may be at least one epoxy based resin, polyester based resin, phenol based resin, and the like, and preferably polyvinyl butyral phenol resin. The mixture can be any combination of thermoplastic and thermosetting resins. The proportion of matrix material in each layer is from about 10% to about 80% by weight of the layer, preferably from 20% to 60% by weight of the layer.

Various amounts of ultraviolet absorber or stabilizer may be added to the fibers or laminated layers to absorb harmful ultraviolet light and to dissipate it into thermal energy. UV absorbers act by shielding fibers or laminated layers from UV light, and UV stabilizers improve the operating life of fibers or laminated layers by scavenging radical intermediates formed during photooxidation when exposed to UV light. It works. Examples of UV absorbers include benzophenones or benzotriazoles from Ciba Specialty Chemicals.

In FIG. 1, a woven fabric with first and second yarns in a first direction and a third yarn in a second direction is shown. In this illustration, the first and second yarns are substantially parallel and intersect with the direction of the third yarn.

<Test method>

In the following examples the following test methods were used.

Linear density . Based on the procedures described in ASTM D 1907-97 and D885-98, linear density is determined by weighing a yarn or fiber of known length. Decitex or "dtex" is defined as the weight (g) of yarn or fiber 10000 m.

Area density. The area density of the fabric layer is determined by measuring the weight of each single layer of the selected size (eg 10 cm × 10 cm). The area density of the composite structure is determined by the sum of the area densities of the individual layers.

Bulletproof penetration. In accordance with NIJ Standard, published in September 2000-0101.04, "Balletproofing of Personal Ballistic Protective Clothing," a V50 ballistic test of multilayer panels is performed. This test discloses using only 9 mm bullets, but we tested equally with 9 mm and also .357 bullets.

The invention will now be illustrated by the following specific examples. Unless otherwise specified, all parts and percentages are by weight. Examples prepared according to the method or methods of the invention are indicated by numbers. Control groups or comparative examples are shown in alphabetical order.

Example  Manufacture and test

In the examples below, multiple layers of woven fabrics were prepared with various combinations of aramid and polybenzoxazole (PBO) yarns in both warp and weft directions. Aramid yarn is under the trade name Kevlar (registered trademark). It was purchased from EI du Pont de Nemours and Company. Aramid was poly (p-phenylene terephthalamide). Polybenzoxazole (PBO) yarn was purchased from Toyobo Co., Ltd. under the trade name Zylon®. The composite of the plurality of fabric layers was tested for ballistic penetration. For each test, all fabric layers were constructed around ballistic panel 16 in ² (40.6 cm 2), sewn around the edges and also sewn diagonally using crossstitch. Several different fabrics were made from materials and yarns of different linear density and tested at various area densities from 3.7 to 6.0 kg / m 2.

Example  One

In Example 1, the 440 dtex Kevlar® 129 and 550 dtex Xylon® yarns were rotated in both warp and weft directions (ie, Kevlar® yarn / Xylon® yarn / 44 layers of fabric were plain weave with 10.2 yarns per cm with Kevlar® yarn / Xylon®, and the area density was about 4.7 kg / m 2.

compare Example  A

In Comparative Example A, 44 layers of fabric were woven by weaving 550 dtex Xylon® yarn with 9.8 yarns per cm and 129 dtex Kevlar® 129 yarns in warp direction at 11.0 yarns per cm. It was prepared, and the area density was about 4.7 kg / ㎡.

compare Example  B

In Comparative Example B, 440 dtex Kevlar® 129 yarns were weaved with 11.0 yarns per cm, 550 dtex Xylon® yarns in the warp direction at 9.8 yarns per cm to 44 layers of fabric. It was prepared, and the area density was about 4.7 kg / ㎡.

The layers of the fabrics of Example 1, and Comparative Examples A and B were tested for ballistic V50 for 9 mm and .357 mag bullets. The ballistic test results shown in Table 1 below show that the V50 results of the articles of the invention shown in Example 1 were significantly better than the V50 results of the articles of Comparative Examples A and B. In summary, the articles of the present invention have improved about 3% to 8% ballistic V50 over the articles of Comparative Examples A and B.

Example  2

In Example 2, 440 dtex Kevlar® 129 and 550 dtex Xylon® yarns were weaved 35 layers of fabric with 10.2 threads per cm in alternating order in both warp and weft directions, with an area density of About 3.7 kg / m 2.

Comparative Example C

In Comparative Example C, 35 layers of fabric were woven by weaving 550 dtex Xylon® yarn with 9.8 threads per cm in a warp direction at 440 dtex Kevlar® 129 threads in 11.0 threads per cm. It was prepared, and the area density was about 3.7 kg / ㎡.

compare Example  D

 In Comparative Example D, 35 layers of fabric were woven with 129 dtex Kevlar® 129 yarns in a weft direction with 550 dtex Xylon® yarns in the warp direction at 11.0 threads per cm in 9.8 threads per cm. It was prepared, and the area density was about 3.7 kg / ㎡.

The layers of the fabrics of Example 2, and Comparative Examples C and D were tested for ballistic V50 for 9 mm and .357 mag bullets. The ballistic test results shown in Table 2 below show that the V50 results of the articles of the invention shown in Example 2 were significantly better than the V50 of articles of Comparative Examples C and D.

Example  3

In Example 3, 1110 dtex Kevlar® 129 and 1110 dtex Xylon® yarns were weaved 36 layers of fabric with 7.5 threads per cm in alternating order in both warp and weft directions, with an area density of About 6.0 kg / m 2.

compare Example  E

In Comparative Example E, 36 layers of the fabric were woven by weaving 1110 dtex Xylon® yarn with 7.5 threads per cm in a warp direction at 1110 dtex Kevlar® 129 threads at 7.5 threads per cm. It was prepared, and the area density was about 6.0 kg / ㎡.

The layers of the fabrics of Example 3 and Comparative Example E were tested for ballistic V50 for 9 mm and .357 mag bullets. The ballistic test results shown in Table 3 below show that the V50 results of the articles of the invention shown in Example 3 were significantly better than the articles V50 results of Comparative Example E.

Example  4

In Example 4, the structures of Examples 1-3 could be replicated with fibers selected from polyarenazole, polypyridazole, polypyridobisimidazole or any combination thereof, instead of Kevlar® fibers.

Example  5

In Example 5, the structures of Examples 1-3 could be replicated with fibers selected from polyarenazole, polypyridazole, polypyridobisimidazole or any combination thereof, instead of xylon® fibers. .

Although the present invention has been described with respect to the preferred embodiments, it should be understood that other similar embodiments may be used, or that the described embodiments may be modified and added to perform the same functions of the invention without departing from the invention. Thus, the present invention should not be limited to any single embodiment, but rather should be construed in the spirit and scope in accordance with the appended claims.

All patents and documents disclosed herein are incorporated by reference in their entirety.

Claims (20)

A first plurality of yarns and a second plurality of yarns, wherein each of the first and second yarns is disposed in a first direction parallel or substantially parallel to the other first and second yarns, and Each third yarn comprises a third plurality of yarns disposed in a second direction parallel or substantially parallel to the other third yarns, where the second direction intersects the first direction and the third threads And the first yarns or the second yarns are made of the first polymer; The specific strength of each of the first, second and third yarns is at least 15 g / dtex; (i) the second yarns are made of a second polymer different from the first polymer, (ii) the average linear density of the first yarns is different from the average linear density of the second yarns, or (iii) the first and second yarns are filaments Fiber layer for use in a penetration resistant article, wherein the filaments of the first yarns differ from the filaments of the second yarns, or (iv) are combined. The method of claim 1, Each of the fourth yarns further comprises a fourth plurality of yarns arranged in a second direction parallel or substantially parallel to the third yarns, (i) the fourth yarns are made of a second polymer or a third polymer, (ii) the average linear density of the third yarns is different from the average linear density of the fourth yarns, or (iii) the third and fourth yarns A fibrous network layer comprising multifilament yarns with filaments, wherein the average linear density of the filaments of the third yarns is different from the filaments of the fourth yarns, or (iv) they are combined. The fiber network layer of claim 1 wherein the first yarns comprise at least 35% of the total number of yarns in the first direction and the second yarns comprise at least 35% of the total number of yarns in the first direction. The fiber network layer of claim 2 wherein the third yarns comprise at least 25% of the total number of yarns in the second direction, and the fourth yarns comprise at least 25% of the total number of yarns in the second direction. The fiber network layer of claim 1, wherein the area density is 10 kg / m 2 or less. The fiber network layer of claim 2, wherein the elongation at break of each of the first, second, third and fourth yarns is at least 2% and the elastic modulus is at least 150 g per dtex. The fiber network layer of claim 1, wherein the second yarns are made of a second polymer different from the first polymer. The fiber network layer of claim 1 wherein the average linear density of the first yarns is different from the average linear density of the second yarns. The fiber network layer of claim 1 wherein the first and second yarns comprise multifilament yarns with filaments, and wherein the average linear density of the filaments of the first yarns is different from the filaments of the second yarns. The method of claim 1, The first and third yarns are made of the first polymer and have the same average linear density, the filaments of the first and third yarns have the same average linear density, And the second and fourth yarns are made of the second polymer and have the same average linear density, and the filaments of the second and fourth yarns have the same average linear density. The fiber network layer of claim 2, wherein the line density of the filaments of the first, second, third, and fourth yarns is between 0.1 and 10 dtex. The fiber network layer of claim 1, wherein the first and second yarns are arranged in alternating order. 3. The fiber network layer of claim 2, wherein the third and fourth yarns are arranged in alternating order. The process of claim 1 wherein the first and second polymers are polyamides, polyolefins, polybenzoxazoles, polybenzothiazoles, poly {2,6-diimidazo [4,5-b: 4 ', 5'-. e] fiber network selected from the group consisting of pyridinylene-1,4- (2,5-dihydroxy) phenylene}, polyarenazole, polypyridazole, polypyridobisimidazole and mixtures thereof layer. A flexible, penetration resistant article comprising a plurality of fiber network layers of claim 1. The flexible penetration resistant article of claim 15, wherein the area density is 2 to 12 kg / m 2. A flexible ballistic article comprising a plurality of layers of fabric with two different types of yarns arranged in alternating order in both the warp and weft directions of the fabric. 18. The flexible ballistic article of claim 17, wherein at least one of the fabric layers is impregnated with a polymer matrix comprising a thermoset resin, a thermoplastic resin, or a mixture thereof. A first plurality of yarns and a second plurality of yarns in which the first and second yarns are arranged in a first direction parallel or substantially parallel to the other first and second yarns; Weaving the third plurality of yarns with each third yarn disposed in a second direction parallel or substantially parallel to the other third yarns, where the second direction intersects with the first direction and , The third yarns, and the first yarns or the second yarns are made of the first polymer; The specific strength of each of the first, second and third yarns is at least 15 g / dtex, (i) the second yarns are made of a second polymer different from the first polymer, (ii) the average linear density of the first yarns is different from the average linear density of the second yarns, or (iii) the first and second yarns A method of forming a fiber network comprising multifilament yarns with filaments, wherein the average linear density of the filaments of the first yarns is different from the filaments of the second yarns, or (iv) are combined. The method of claim 19, Weaving a plurality of yarns in which each of the fourth yarns are disposed in the second direction parallel or substantially parallel to the third yarns, (i) the fourth yarns are made of a second polymer or a third polymer, (ii) the average linear density of the third yarns is different from the average linear density of the fourth yarns, or (iii) the third and fourth yarns are Multifilament yarns, wherein the average linear density of the filaments of the third yarns is different from the filaments of the fourth yarns, or (iv) they are combined.

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